Wilke



1961 G. WILKE 3,014,928

CYCLODODECADIENE MONOEPOXIDE, AND ITS PRODUCTION FROM CYCLODODECATRIENESFiled April 25, 1958 INVENTOR GUI/THEE WILKE Sta Filed Apr. 23, 1958,Ser. No. 730,339 Claims priority, application Germany Apr. 26, 1957 11Claims. (Cl. 260-348) This invention relates to cyclododecadienemonoepoxide, and its production from cyclododecatriene.

Belgian patent specification No. 555,180 describes a process which isconcerned with the production of cyclododecatri-(l,S,9)-enesconcurrently with other cyclic hydrocarbons from butadiene and otherdiolefines. With the aid of organometallic mixed catalysts, such as havebeen developed by K. Ziegler and collaborators for the polymerisation ofethylene, it is possible by means of this process to obtaincyclododecatri-(1,5,9)-enes in various configurations and with highyields (namely 8090%) from butadiene, for example. -It has been pointedout in said Belgian patent that these cyclododecatrienes are valuablestarting materials for organic syntheses, especially for the productionof a,w-difunctional derivatives of n-dodecane.

It is known that cyclic hydrocarbons can be converted by oxidation intodifunctional open-chain compounds with the same number of carbon atoms.Such a process has for example been achieved in the oxidation ofcyclooctane to suberic acid. These ring-splitting reactions can howeveronly be carried out with good yields if it is possible for the cyclichydrocarbon to be converted, prior to the splitting reaction proper,into a monofunctional or 1,2-difunctional oxidation product, for exampleinto an alcohol or a glycol, since in this case the splitting reactiontakes place preferentially on the carbon atoms already combined withoxygen. Thus, suberic acid is obtained in a high yield from cyclooctanolby means of nitric acid.

Consequently, in the conversion of cyclododecatriene into thea,w-difl.InCiiOI1fll derivatives of n-dodecane, an attempt must be madeto convert the triply unsaturated ring in the first reaction stage intoa definite derivative with only one oxygen function in the molecule. Atfirst sight the simplest method seems to be the selective hydro genationto cyclododecene, which can then be converted in known manner intocyclododecanol. This process would correspond to the reaction sequencewith cyclooctatetraene, which, as indicated by W. Reppe andcollaborators, can easily be converted into cyclooctene by selectivehydrogenation.

The selective hydrogenation cannot however be carried out withcyclododecatriene, since the latter differs very substantially fromcyclooctatetraene by the fact that the double bonds in the molecule arenot conjugated double bonds, an arrangement which is essential for thehydrogenation to form a monoolefine, for it is only in this case thatthe last double bond of the polyoleiine is hydrogenated very much moreslowly than the others. When cyclododecatri(1,5,9)-ene is hydrogenated,a mixture of cyclododecene With cyclododecane and cyclododecadiene isalways obtained, since the double bonds do not differ, or only differslightly, in their hydrogenation capacity.

It has now been found that cyclododecatriene can be converted simplywith high yields into the desired monofunctional derivative byconverting the cyclododccatriene into cyclododecadiene monoepoxide. Inaccordance with the invention, cyclododecatrienes of any desiredconfiguration, but specially the trans-trans-cis-configuration and thetrans-trans-trans-configuration, are oxidised with or- 3,014,928Patented Dec. 26, 1961 ice when no excess of per compounds is used, theformation velocity of this monoepoxide clearly being very much greaterthan the formation velocity of the diepoxides or triepoxides. As percompounds, it is possible to use per acids, such as performic acid,peracetic acid, trilluoroperacetic acid, perbenzoic acid or acetaldehydeperacetate.

It is particularly advantageous to use acetaldehyde peracetate, which isformed under certain conditions when acetaldehyde is oxidised and can beutilised in accordance with British Patent No. 735,974 for epoxidationpurposes. By using this per-compound, the cyclododecadiene monoepoxideis obtained with a yield higher than and in addition acetaldehyde andacetic acid are recovered. This process can be carried out continuouslyparticularly smoothly.

It is advisable to avoid an excess of per-compounds. The best resultsare produced when a deficiency of percompounds is used. The oxidation isadvantageously carried out at temperatures from 0 to 0, preferably from20 to 50 C., in a solvent which is inert with respect to per-compounds.Aliphatic or aromatic hydrocarbons, or their halogen or oxygenderivatives, can for example be used as such inert solvents. v

In the process of the invention, high yields of cyclododecadienemonoepoxide are obtained as well as small proportions of themonoacylates of cyclododecadienediol, which are formed due to conversionof the initially formed epoxide by the acid which is present or which isformed. These by-products are however also valuable, since they caneasily be converted into the cyclododecanediol, which can be used withequal success for the ring-splitting reaction.

The cyclododecadiene monoepoxide obtained by the process of theinvention can be hydrogenated selectively to cyclododecane epoxide orcompletely to cyclododecanol. The cyclododecanol can be oxidised tocyclododecanone. The cyclododecanone can'in its turn be converted inknown manner into its oxime and the latter by Beckmann transformationinto the lactarn of w-aminododecane carboxylic acid. It is known thatthe'lactam is an important initial material for the production ofpolyamide plastics.

The cyclododecanol can also be split, for example with nitric acid, toform dodecane-1,12-carboxylic acid, which also is an important materialfor the production of polyamides and polyesters.

The following examples further illustrate the invention.

Example 1 44 g. of 68% peracetic acid are added dropwise over a periodof 1 /2 hours to a solution of 134 g. of cyclododecatriene in 462 g. ofchloroform, the temperature being kept between 25 and30 C. by cooling.After the dropwise addition is complete, almost the whole of theperacetic acid has reacted. After the reaction mixture has been washedwith a bicarbonate solution and the solvent removed, distillation of theresidue yields 45.6 g. of cyclododecadiene epoxide, RP. 05 mm, 68-71 C.,n 1.5060, as well as unmodified cyclododecatriene. The yield is 97% ofthe theoretical, based on reacted cyclododecatriene, and 64% of thetheoretical, based on peracetic acid.

Example 2 The procedure is as set out in Example 1, but a mixture ofglacial acetic acid and acetic acid anhydride (5:1) is used as solvent.The yield is 93% of the theoretical, based on reacted cyclododecatriene,and 72% of the theoretical, based on peracetic acid.

Example 3 8.5 g.=(0.05 mol) of cyclododecatriene, dissolved in 10 cc. ofchlorobenzene, are mixed at C. with 250 cc. of a solution of perbenzoicacid in chlorobenzene which titres 14.1 cc. of N/ 10 Na S O per 10 00.,this corresponding to 0.35 mol of perbenzoic acid. The solution isslowly heated to room temperature and left to stand for 2 hours, afterwhich it is no longer possible to detect any peracid. The chlorobenzeneis distilled oil in vacuo and the residue is fractionated. 3.9 g. ofcyclododecadiene epoxide are obtained, this corresponding to a yield of65% of the theoretical.

Example 4 45.2 g. of acetaldehyde mono-peracetate, dissolved in 140 g.of glacial acetic acid, are added dropwise over a period of 50 minutesto 120 g. of trans-trans-cis-cyclododecatri-(1,5,9)-ene. The temperatureis kept below 10 C. The reaction mixture is stirred for another 3 hoursand thereafter the solvent is distilled off in vacuo. Fractionation ofthe residue through a highly effective column at 13 mm. Hg yields 44.4g. of cyclododecadiene epoxide, RP 13 mm 133.8-1342" C.; i7 :1.5060. Theyield is 83% of the reacted cyclododecatriene, or 66.5% based on theacetaldehyde mono-peracetate.

The infra-red spectrum of the epoxide produced is shown on the left handside of the accompanying drawmg.

Example 5 The procedure is as set out in Example 4, except thattrans-trans-trans-cyclododecatri-(1,5,9,)-ene, dissolved in glacialacetic acid, is used for the epoxidation. A similar yield ofcyclododecadiene epoxide is obtained; the infrared spectrum of theproduct, as shown on the right hand side of the accompanying drawing,still gives an indication of the absorption due to a cis-double bondonly in the middle position. B.P. mm 71-73" C.; 11 1.4995; M.P. 26-27 C.

Example 6 The procedure set out in Example 4 is used, but ethyl acetateis used as solvent, and the reaction temperature is kept between 25 and30 C. The reaction is complete after only 1 hour. The yield is 92%,based on reacted cyclododecatriene, and 78% of the theoretical, based onacetaldehyde monoperacetate.

Example 7 The continuous epoxidation of cyclododecatri-(1,5,9)- ene withacetaldehyde peracetate is carried out as follows: A solution ofacetaldehyde monoperacetate in ethyl acetate is continuously mixed at 5to C. with a solution of cyclododecatriene in acetic ester (molar ratiobetween cyclododecatriene and peracetate 2:1). The cold mixture isintroduced by suction into a separating column which is kept at 40-50"C. and which is under a vacuum of 30 to 50 mm. Hg. The separating columnserves as reactor. Acetaldehyde, ethyl acetate and the glacial aceticacid which is formed are drawn off through the head of the column. Thereaction product and unreacted cyclododecatriene are withdrawn from thelower part of the column and are separated from one another by beingre-distilled in vacuo.

This procedure gives the cyclododecadiene epoxide in yields higher than90% of the theoretical, based on reacted cyclododecatriene. Theunreacted cyclododecatriene, and the ethyl acetate and the acetaldehydeare returned to the cycle.

Example 8 The procedure followed is that set out in Example 3, buthexane is used instead of chlorobenzene as solvent. The yield ofcyclododecadiene epoxide is 85% of the theoretical, based on reactedcyclododecatriene, and 70% of the theoretical based on perbenzoic acid.

Example 9 215 g. of formic acid are run into vigorously stirred mixtureof 1,300 g. of cyclododecatriene and 1,350 g. of 25% hydrogen peroxide.After a time, the internal temperature rises and the temperature is keptbelow 35 C. by cooling with ice and later with water. The mixture isstirred for 48 hours, whereupon the resulting two layers are separatedand the organic layer is washed with water, dilute sodium hydroxidesolution and bisulphite solution and dried over CaCl Distillation bymeans of an efiicient column yields 520 g. of unreactedcyclododecatriene, 846 g. of 1,Z-epoxycyclododecadi-S,9-ene and 12 g. ofresidue, i.e. a yield of 98% of the theoretical is obtained, with aconversion of 60%.

What I claim is:

1. 1,Z-monoepoxycyclododeca-di-(5,9)-ene.

2. Process for the production of 1,2 monoepoxycyclododeca-di-(5,9)-enewhich comprises oxidizing cyclododecatri-(l,5,9)-ene at a temperaturebetween about 0 and 100 degrees C. with an oxidizing agent selected fromthe group consisting of acetaldehyde, monoperacetate, performic acid,perbenzoic acid and peracetic acid.

3. Process according to claim 2 in which said cyclododecatri-(1,5,9)-eneis in the form of the trans-transsis-isomer.

4. Process according to claim 2 in which said cyclododecatri(l,5,9)-eneis in the form of the trans-transtrans-isomer.

5. Process according to claim 2 in which said oxidizing agent isperformic acid.

6. Process according to claim 2 in which said oxidizing agent isperacetic acid.

7. Process according to claim 2 in which said oxidizing agent istrifiuoroperacetic acid.

8. Process according to claim 2 in which said oxidizing agent isperbenzoic acid.

9. Process according to claim 2 in which said oxidation is effected at atemperature between about 20-50 degrees C.

10. Process according to claim 2 in which said oxida tion is effected inthe presence of an inert organic solvent.

11. Process according to claim 2 in which saidcyclododecatri-(1,5,9)-ene in solution in ethylacetate is mixed withacetaldehyde peracetate at a temperature below about 0 degree C. andthereafter oxidation is elfected by raising the temperature of themixture to between about 40-50 degrees C.

References Cited in the file of this patent UNITED STATES PATENTS2,201,200 Pinkey May 21, 1940 2,221,369 Cass Nov. 12, 1940 2,250,445Bruson July 29, 1941 2,281,253 Susie Apr. 28, 1942 2,351,352 McAllisterJune 13, 1944 2,359,935 Nudenberg Oct. 10, 1944 2,426,224 Kharasch Aug.26, 1947 2,438,485 Henne Mar. 23, 1948 2,500,599 Bergsteinsson et alMar. 14, 1950 2,524,432 Dorough Oct. 3, 1950 2,541,670 Segall Feb. 13,1951 2,752,376 Julian et al. June 26, 1956 FOREIGN PATENTS 192,907Austria Nov. 11, 1957 OTHER REFERENCES Findley et al.: JACS, vol. 67,pages 412-414 (1945). Swern: JACS, vol. 69, pages 1692-1698 (1947).Swern: Chem. Reviews, vol. 45, pages 1-68 (1949). Prolog: Helv. Chim.Acta 38, 1955, pp. 1786-94.

1. 1,2-MONOEPOXYCYCLODODECA-DI-(5,9)-ENE